Adhesive of the remoistening type



Patented Nov. 12, 1940 UNITED STATES imam PATENT OFFICE ADHESIVE OF THE BEMOISTENING TYPE Hans-F. Bauer, Chicago, Jordan V. Bauer, Elm.-

wood Park, and Don M. Hawley, Geneva, 11]., assignora to Stein, Hall Manufacturing Oom- No Drawing.

Chicago, 11L, a corporation of Delaware Application January 28, 1939, Serial No. 253.344

13 Claims. (Cl. lac-23.4)

247,138, died December. 22, 1938.

The term 'famylaceous adhesive is employed herein to refer to those types of adhesives which are prepared from starches and starch degradation products, such as dextrines or starch gums. The expression remoistening adhesive is employed to describe an adhesive which is applied to a material as a coating and dried, and which,

on being moistened, will develop tacklness and act as a suitable adhesive for bonding the material to other materials.

At present, large amounts of gummed paper, suitable for such purposes as labels, stamps and envelope seals, are prepared with dextrine adhesives, but dextrine adhesives have never been successful in replacing animal glue adhesives in the field of gummed tape for sealing the heavier types of boxes or for gummed paper or fabric which is to be used for purposes wherein it is required that the adhesive coating on being moistened will develop rapidly strong adhesive properties and set up very rapidly to form ,a bond. In

1 our applications previously referred to, we have described new and improved types of adhesives made, from base materials of certain specified characteristics, intimately dispersed or associated with certain auxiliary materials. We have also described new and improved types of gummed tapes made from such adhesives.

These adhesives afiord many improvements and advantages over the animal glue type of adhesive and possess remoistening adhesive properties which are superior to most of the animal glue adhesives now in use. They canvbe employed in these uses where heretofore only gummed tape made from animal glue or fish glue remoistenlng adhesives could besatisfactorlly used.

In carrying outthe inventions describedin the aforesaid patent applications, we have stressed particularly the use oi urea or of a water soluble .urea, in conjunction with the starchier types of amylaceous conversion. products, the urea acting as a plastieizing agent and at the same time counteracting the retrogradation oi incompletely degraded vportionsiof the amylaceous base material to a less soluble form.

One of the objects of this invention is to provide new and improved types of remoistening ad hesives, characterized by exceptional adhesive strength and suitable for the strongest type of remoistening applications. Other objects will appear hereinafter.

In accordance with this invention it has been found that water soluble thiocyanates, which have a solubilizing or dispersing action on starch degradation products, may be employed in amylaceous adhesive compositions made from the starchier types of amylaceous conversion products and are adapted to act as plasticizing agents and to counteract the retrogradation of incompletely degraded'portionsof the amylaceous material to a lesssoluble form.

We have found, in accordance with this invention, that by employing water soluble thiocyanates in the manner hereinafter more specifically disclosed we are able to prepare superior remoistening adhesives which develop extreme tackiness immediately upon being remoistened, do not-tend to slip or slide on the surface to which they are applied even under conditions of considerable tension or sidewise pressure and have suflicient cohesiveness while still wet to hold surfaces together which. would normally tend to spring apart.

Our base materials, for the purpose of this invention, comprise the starchier types of a'mylaceous' conversion products which have been converted to the-following characteristics:

(a) A. dextrine content of less than 55%,.as determined by the method of Babington, Tingle and Watson, Journal bf the Society of Chemical Industry 3711918) 257. This method is as follows:

The sample (1 gm.) is warmed in a 100 cc. graduated flask with 30 cc. of water until just gelatinized and cooled quickly; 50 cc; of acold saturated barium hydroxide solution isnext added (the flask being meanwhile shaken), followed by enough water to bring the total volume to 100 cc. The solution is filtered through a'drv 15 cm. paper and an aliquot portion (50 cc.) 0; the :flltrate pipetted into a platinum dish. After the addition of Zdrops of 1% phenolphthalein soluexpose the maximum surface to the air, after which the dish is transferred to a well regulated oven and dried to constant weight at 120 0., below which temperature crystallized barium chloride is dehydrated. Dextrin gum being hygroscopic, precautions must be taken accordingly. The dish is now heated strongly, but not beyond the temperature necessary for the complete combustion of the organic matter. During ignition the sand should The well stirred at intervals to allow full exposure to the air. The dish and contents are then cooled and weighed. The difierence in weight before and after ignition represents the dextrin gum in 50 cc. of filtrate, i. e., in half the weight of sample taken.

(b) The viscosity of degraded or dextrinized starches is a definite indication of the extent to which the starch has been dextrinized or degraded. A suitable conversion product for the purpose of this invention comprises a dextrinized or degraded starch which when cooked in the proportions of 1 part of conversion product to 1% parts of water to 190 F. and then cooled to 125 F. gives a viscosity reading within the range of 15 seconds to 400 seconds, preferably within the range of 25 seconds to 150 seconds on a Stormer viscosity apparatus, the readings in question being the'time for 100 revolutions of the 'viscosimeter cylinder using a 100 gram weight. The Stormer viscosimeter used gave a reading of 5.6 seconds'with water at 125 F. and a reading of 2.4 seconds running free with the viscosimeter cup empty, these readings 'being the time required for 100 revolutions of the viscosimeter cylinder using a 100 gram weight.

Within the limits given under '(a) and (b) we preferably employ the following types of conversion products:

(1) British gums having a solubility greater than about 60%,, preferably 70% to 95%, in water at 75 F., and

(2) Incompletely dextrinized starches of the white dextrine type having a solubility in water from about 3% to about 50% at 75 F.

The term British gum" is employed to refer to those types of starch degradation-products that are formed by roasting or heating starch without, or at the most, with very small amounts of acid catalysts as differentiated from dextrines which "are formed from starch by roasting or heating the starch with relatively large amounts of acid catalysts. For the purpose of this invention it is preferable to employ as the base material a British gum type of amylaceous conversion product, but it will be understood that any amylaceous material having the general characteristics given under (a) and (b) may be employed in conjunction with the auxiliary materials mentioned hereinafter under (d) for the purpose of making a remoistening adhesive according to this invention.

(d) The base material given under (a) and (b) is mixed with or dispersed with a water soluble thiocyanate, preferably with the influence of'heat, the thiocyanate being employed in effective amounts to plasticize the composition and to counteract the retrogradation of the more incompletely degraded portions of the amylaceous base material to a lesssoluble form. Among the water soluble thiocyanates which may be employed are ammonium thiocyanate, sodium thiocyanate and potassium thiocyanate. As previously indicated, the thiocyanates in addition to having a solvent action on starch conversion products apparently act as plasticizing agents, tending to inhibit the formation of checks or cracks, and they may be used either alone or in conjunction with other materials having a similar solvent and plasticizing action, as for example, water soluble ureas, including urea and thioureaand/or water soluble nitrates, including potassium nitrate, sodium nitrate, calcium nitrate and guanidine nitrate, with or without additional plasticizing agents, as, for example, glycerine, ethylene glycol, diethylene glycol and other polyhydric alcohols, or with sodium lactate and other substances having a plasticlzing effect although not necessarily having a solvent eflect on starch conversion products. In general it is preferable to employ about 3% to about 30% of a water soluble thiocyanate, with or without about 1% to about 10% ofa plasticizer, such as glycerine, polyhydric alcohols or other normally liquid plasticizers.

(e) In addition to the foregoing auxiliary materials a relatively small amount of a viscosity increasing agent for amylaceous dispersions may be employed to improve the result obtained. A preferred agent for this purpose is borax. Sodium aluminate and similar soluble aluminates function somewhat similarly to borax in increasing the viscosity of amylaceous dispersions. The viscosity increasing agent may also be formed in situ in the adhesive composition, for example, i

by incorporating boric acid in the adhesive and adding an alkali in the remoistening water or a some other compound adapted to react with boric acid to form a soluble borate.

The amount of borax or other viscosity increasing agent is preferably less than about 5% (e. g. about 1% to about 5%) and preferably not gerater than the amount of plasticizer. Where borax is employed in the compositions of this invention, it is preferable to employ a plasticizer havinga modifying action on borax. Without such a plasticizer borax has an insolubilizing action on the starchier types of conversion products used as base materials which tends to destroy the retack properties.

It may be observed that thewatei' soluble thiocyanates apparently have a modifying action on borax, which inhibits the insolubilizing action of the borax on the amylaceous conversion products. Hence, according to this invention, remoistening adhesives'may be prepared from base materials having the general characteristics given under (a) and (b), together with borax and a solvent-plasticizing agent such as a water soluble thiocyanate, which is normally solid, with or without a plasticizing agent such as glycerine, which is normally liquid.

By the use of the specifically defined combination of materials herein disclosed, remoistening adhesives may be produced which are at least equivalent in adhesive properties to the better grades of animal glue remoistening adhesives. Additionally, it has been found that by the introduction of borax or other viscosity increasing agent into the water used to remoisten the adhesive him, it is possible to obtain adhesive results far superior to animal glue remoistening adhesives.

- The following examples in which the quantities are statedin parts by weight will illustrate several of the preferred adhesive formulae of this invention and a comparison of their adhesive properties with other types of remoistening ad-' Y delphia, Pennsylvania, U. S, A. It will be understood that the results of these tests may vary aaaaosa somewhat depending upon humidity and temperature conditions, but the comparative results deflnitely showed the superiority oi adhesives made in accordance with this invention.

'limmplel Parts Tapioca British gum; 97 Borax 3 Potassium thiocyanate .Water 110 Example I! Parts Tapioca conversion product 97 Borax 3 30 Potassium thiocyanate 15 .Water The above materials were mixed together and cooked to a temperature of about 180 F. The

a mixture was then cooled to 80 F. and applied to P p r tap and dried.

Example III Parts Tapioca British gum oi! Example I. 97 Sodium thiocyanate 2 Urea 4 15 Borax 3 Glycerine 2 .water 110 The adhesive was prepared as in Example I and on applied to paper tape on a small scale gumming machine adapted to produce results similar to those obtained on large scale machines. The

maximum test averaged about 92.3. A higher test was obtained when the tape was moistened 65 with a saturated solution of borax.

Example IV I I A Parts Tapioca conversion product of Example II 97 Potassium thiocyanate 2 Borax I 3 Urea 15 Glycerine 2 Water 110 7 The adhesive was prepared as in Example 11 was moistened with a saturated solution of borax.

Less desirable results are obtained with starches The tapioca conversion product used was one having a dextrine content McLaurin tests on this tape averaged about 82.

Higher tests were obtained when the tape was moistened with a saturated solution of borax.

It should be understood that the examples of adhesive formulae given above are for the purpose of illustrating the novel character of the invention and for the purpose of making clear the principles and the relative value of the means by which the result is obtained. It is not desired to limit the invention by the specific examples, inasmuch as numerous variations may be made in the character of the adhesive base and in the proportion of other ingredients used without departing from the limits defined as essential for the purpose of the invention.

The starches employed may be derived from root starches, for example, tapioca, sago, cassava, potato. and sweet potato, or from grain starches, for example, corn, rice and wheat. In general, conversion products made from the root starches are preferred and give the best results regardless of whether the conversionproduct is an incompletely dextrinized product or a British gum.

derived from grains, particularly where the conversion product is a dextrine or an incompletely dextrinized starch rather than a British gum.

Various plasticizing agents, wetting agents, solvents, anti-foam agents and filling materials may be used in conjunction with the preferred adhesive means for the purpose of outlining those special eil'ects for which the use of such materials is known to the adhesive art. Small amounts of sulionated oils, as, for example, Turkey red oil, in proportions oi, say, (1.5% to about 3% may be included in the adhesive compositions of this invention.

In such instances where it is desirable, the disclosed adhesive compositions maybe mixed with compatible adhesive materials made from animal glue, fish glue, casein, starch, natural gums and water soluble natural or synthetic resins.

Adhesive compositions made in accordance with the present invention, when applied as a coating 4 and dried and thereafter remoistened, develop exi treme tackiness immediately and are characterized by a-very high rapidity of set. As contrasted with animal glue adhesives, they have practically no odor. One ofthe further features of the invention resides in the fact that the preferred adhesives are substantially neutral and contain no ingredients which are harmful to paper or fabric. In addition, adhesive films prepared as we have described, are extremely flexible and do not readily check, crack or chip off from the material to which they are applied.

Adhesive compositions of this type may be used not only as moistening adhesive on 'gummed .tape or other sheet materials, but also in other less than as determined in the manner herein described, a fluidity within the range of about 15 seconds to about 400 seconds, as determined in the manner herein described. a water solubility at 75 F. within the range of 70% to 95%, intimately dispersed with about 1% to about 5% borax, about 3% to about 30% of an alkali metal thiocyanate, and about 1% to about glycerine, the amount of glycerine being greater than the amount of borax.

2. A remoistening adhesive composition formed 10 from a British gum having a solubility in water at 75 F. of about 60%, a dextrine content .less

than about 55%, as determined in the manner herein described, and a fluidity within the range of about seconds to about 400 seconds, as de- 15 termined in the manner herein described, in-

timately dispersed with a water soluble borate in amounts effective to increase the viscosity but not greater than about 5% by weight of "said British gum and about 3% to about 30% of a plasticizer for said adhesive having amodifying action on said borate and comprising a water soluble thiocyanate, said adhesive possessing strong adhesive properties and being capable of forming dried flexible coatings, which, when moistened, develop tackiness and set to a strong bond rapidly.

3. A remoistening adhesive composition formed from a root starch converted to a solubility of 3% to about 50% in water at 75 F., a viscosity within 9 the, range of about 15 seconds to about 400 seconds, as determined in themanner herein described, and a dextrine content less than about 55%, as determined in the manner herein described, intimately dispersed with a water soluble borate in amounts less than about 5% and about 3% to about 30% of aplasticizing agent comprising a water soluble thiocyanate, said adhesive possessing strong adhesive properties and being capable of forming dried flexible coatings, which,

when moistened, develop tackiness and set to a strong bond rapidly.

4. A remoistening adhesive composition comprising an amylaceous conversion product having a dextrine content less than about 55%, as

determined in the manner herein described, and a fluidity within the range of about 15 seconds to about 400 seconds, as determined in the manner herein described, intimately dispersed and associated with a water soluble thiocyanate in amounts from about 3% to about 30% by weight of the amylaceous conversion product, said adhesive possessing strong adhesive properties and being capable of forming dried, flexible coatings, which when moistened develop tackiness and set rapidly. T

5. A remoistening adhesive formed from a British gum having a dextrine content less than about 55%, as determined in the manner herein described, a fluidity within therange of about- 15 seconds to about 400 seconds, as determined.

in the manner herein described, and a solubility of at least 60% in water at 75 F., intimately dispersed with a water soluble borate normally having an insolubilizing action on said British gum in effective amounts to increase the viscosity of said adhesive, and a normally solid plasticizer for .said adhesive comprising a water soluble thiocyanate and having a solubilizing action on said British gum and a modifying action on said borate in amounts efl'ective in inhibiting the insolubilizing action of said borate on said British gum and in inhibiting retrogradation of said British gum to a' less soluble form, said adhesive possessing strong adhesive properties and being capable of forming dried flexible coatings, which,

when moistened, develop tackiness and set to a strong bond rapidly.

6. A remoistening composition comprising an amylaceous conversion product having a dextrine content of less than 55%, as determined in the 5 manner herein described, and a fluidity within the range of about 15 seconds to about-400 seconds, as determined in the manner herein described, intimately associated with a viscosity increasing agent in efiective amounts to increase 10 the retack properties of said adhesive and a plurality of plasticizing agents efiective to inhibit checks and cracks of dried films of said adhesive, one of said plasticizing agents being normally solid and comprising a water soluble thiocyanate 15 in proportitons from about 3% to about 30% by weight of the conversion product, and another being normally liquid and comprising a polybydric alcohol in proportions from about 1% to about 10% of said conversion product. '20

7. A remoistening adhesive formed from an incompletely dextrinized root starch conversion product converted to a solubility of about 3% to about 50% in water at 75 F., a viscosity within the range of about 15 seconds to about 400 sec- 25 onds, as determined in the manner herein described, and a dextrine content less than about 55%, as determined in the manner herein described, intimately dispersed with a water soluble borate normally having an insolubilizing action 30 on said conversion product in effective amounts to increase the viscosity of said adhesive, and a normally solid plasticizer for said adhesive comprising a water soluble thiocyanate having a solubilizing action on said conversion product and a 35 modifying action on said borate in amounts eflective in inhibiting the insolubilizing action of said borate on the said conversion product and in inhibiting retrogradation of said conversion product to a less soluble form, said adhesive possessing V strong adhesive properties and being capable of forming dried flexible coatings, which, when moistened, develop tackiness and set to a strong bond rapidly.

8. A remoistening adhesive composition com- 45 prising an amylaceous conversion product having a dextrine content less than about 55%, as determined in the manner herein described, and a fluidity within the range of about 15 seconds to about 400 seconds, as determined in the man- ,50 ner herein described, intimately dispersed with a water soluble borate and at least one plasticizing agent, comprising a water soluble thiocyanate, adapted to counteract the retrogradation of incompletely degraded portions of the amy- 55 laceous base material to a less soluble form, said adhesive possessing strong adhesive properties and being capable of forming dried flexible coatings, which, when moistened, develop tackiness and set to a strong bond rapidly. 6o

9. A remoistening adhesive composition comprising an amylaceous conversion product having a dextrine content less than about 55%, as determined in the manner herein described, and

- a fluidity within the range of about 15 seconds 65 to about 400 seconds, as determined in the manner herein described, intimately. dispersed with a viscosity increasing agent for amylaceous conversion product and at least one plasticizing agent comprising a water soluble thiocyanate 7 adapted to. counteract the retrogradation of incompletely degraded' portions of the amylaceous base material to a less soluble form, said adhesive possessing strong adhesive properties and being capable of forming dried flexible coatings. 75

s set to a strong bond rapidly.

10. A remoistening adhesive composition comprising an amylaceous conversion product having a dextrine content less than about as determined in the mannerherein described, and a fluidity within the range of about 15 seconds to about 400 seconds, as determined in the man-- ner herein described, intimately associated with a viscosityincreasing agent in effective amounts to increase the retack properties of said adhesive and at least one plasticizing agent comprising a water soluble thiocyanate in effective amounts to inhibit checks and cracks in dried films of said adhesive, said adhesive possessing strong adhesive properties and being capable of forming dried flexible coatings, which, when moistened, develop tackiness and set to a strong bond rapidly.

11. A remoistening adhesive composition comprising an amylaceous base material composed substantially oi an incompletely dextrinized starch having a dextrine content less than about 55%, as determined in the manner herein described, a fluidity within the range of about 15 seconds to about 400 seconds, as determined in the manner herein described, and a solubility within the range of about 3% to about 50% in water at 'l5 F., intimately dispersed with a plasticizing agent comprising a water soluble thiocyanate in amounts eitective to counteract the retrogradation of incompletely degraded 400 seconds, as determined in the manner hereportions of the amylaceous base material to a less soluble form. a

12. A remoistening composition comprising an amylaceous base material consisting substantialhr of a British gum having a'solubility in water of at least at F. and a dextrine content lessthan about 55%, as determined in the manner herein described, together with a fluidity within the range of about, 15 seconds to about 10 in described, intimately associated with a plasticizing agent in amounts eflfective to counteract the retrogradation of incompletely degraded portions of the amylaceous base material to a less soluble form, and comprising a water soluble thiocyanate.

13. A remoistening adhesive composition comprising an amylaceous conversion product having a dextrine content less than about 55%, as determined in the manner herein described, and 20 a fluidity within the range 01' about 15 seconds to about $00 seconds, as determined in the manner herein described, intimately dispersed with a piasticizing agent in amounts eii'ective to inhibit the retrogradation of incompletely de- 25 graded portions or the amylaceous base material to a less soluble form, said plasticizing agent comprising a water soluble thiocyanate.

me F. Baum. JORDAN v. mum

non u. mwmr. 

